Tetrakisazo dyestuffs soluble in water



Patented Nov. 3, 1942 UNITED STTS TETRAKISAZO DYESTUFFS SOLUBLE IN WATER Adolf Sieglitz and Martin Renter, Frankfort-onthe-Main, Germany, assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application November 14, 1940, Se-

rial No. 365,653. In Germany December 9, 1939 Claims.

The present invention relates to tetrakis-azodyestuffs soluble in water; more particularly it relates to the dyestuffs of the following general formula:

SIOaH l I aH S'OsH l l HzN X N112 wherein X stands for a simple carbon linkage or for one of the groupings CI-I=CH and NHCONH, and wherein the benzene nuclei may contain further substituents, with the same or a different aceto-acetyl compound of the general formula:

CH3.OO.CH2.CO.NH

wherein the benzene nuclei may contain sublstituents and at least one of the two benzene nuclei contains one or more sulfonic acid or carboxylic acid groups.

The dyestufis which are derived from the di- NH O O NH- The dyestufis thus obtained are distinguished by a very good affinity for cotton fibers and regenerated cellulose fibers as well as for mixtures of these fibers and yield yellow and orange dyeings of very good fastness to water and to wash- The aceto-acetyl compounds used as coupling components may be obtained by causing the corresponding amino-azo-compounds to react with diketene.

'The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight:

1. 402 parts of 4.4'-diaminodiphenylurea 3.3'- disulfonic acid are tertzotized in the usual manner. The suspension of the tetrazo-compound is then introduced into a solution of 766 parts of the sodium salt of 4-acetoacetylamino-1.1'-azobenzene-W-sulfonic acid (obtainable by causing diketene to act upon 4-amino-l.1'-azobenzene- 4'-sulfonic acid) and 216 parts of sodium car bonate in water. When the coupling is finished the dyestuif is salted out, filtered with suction and dried. It is a yellow powder which has a very good aflinity for cotton and viscose silk. The yellow dyeings obtained are distinguished by a very good iastness to water and to washing and a good fastness to light. A mixed fabric consisting of parts of cotton and 50 parts of staple fiber from viscose is dyed yellow tone-in-tone' tints. The dyestuif corresponds with the following formula:

SOsH

The same 'dyestuff may be obtained by diazo tizing 436 parts of 4-nitro-1-aminobenzenc-2- sulfonic acid in the usual manner, coupling the diam-compound obtained with 766 parts of 4- acetoacetylamino 1.1 azobenzene 4' -sulfonic acid in a solution rendered alkaline with sodium carbonate, reducing in the usual manner the disazo-dyestuif obtained and transforming the amino-compound obtained with phosgene into urea.

The same dyestuii may be preparedgbymonodiazotizing 376 part of 1.4-diaminobenzenesul fonic acid in the usual manner, combining the diazo-compound with 766 parts of 4-acet0-acetylamino-1.1-azobenzene-4-sulfonic acid in a solution rendered alkaline with sodium carbonate and transforming the disazo-dyestufi thus obtained with phosgene into urea.

2. 402 parts of 4.4-diaminodiphenylurea-3.3- disulfonic acid are tetrazotized in the usual manner and the tetrazo-compound is introduced into an aqueous solution of 854 parts of the sodium salt of 4-acetoacetylamino-2-methoXy-4-methyl-1.1'-azobenzene-3-sulfonic acid and 212 parts of sodium carbonate. The dyestufi' obtained is salted out, filtered with suction and dried. It dyes cotton reddish-yellow tints of very good Iastness to water and to washing and good fastness to light.

Dyestuffs of similar properties are obtained if the acetoacetyl compounds used in the preceding examples are replaced'by 4-acetoacetylamino -2.3- dimethyl -1.1- azobenner. The suspension of the tetrazo-compound is then introduced into 766 parts of the sodium salt of 4-acetoacety1amino-1.1'-azobenzene-4'-sulfonic acid in a solution rendered alkaline with sodium carbonate. The dyestuif is separated by salting out, filtered with suction and dried. It dyes cotton reddish yellow tints of very good fastness to water and to Washing and good fastness to light.

By using as coupling components 4-acetoaicetylamino -2- methoxy-4'-methyl-1.1'-azobenzene-3-sulfonic acid or 4-acetoacetylamino-2'B- dimethyl-1.1'-azobenzene-4'.5 -disulfonic acid instead of 4-acetoacetylamino-1.1-azobenzene-4'- sulfonic acid or as diazo-component 4.4'-diamino 5.5'- dimethyl diphelnyl -3.3'- disulfonic acid dyestufis of similar properties are obtained.

4. 370 parts of 4.4-diaminostilbene-2.2-disulfonic acid are tetrazotized in the usual manner and coupled with 766 parts of the sodium salt of 4-acetoacetylamino l.1'- azobenzene-4-sulfonic acid in a solution rendered alkaline with sodium carbonate. The dyestufi obtained dyes cotton orange tints of very good fastness to water and to washing.

A similar dyestufi is obtained by using 4-acetoacetylamino-l.1'-azobenzene-3carboxylic 'acid as coupling component.

with sodium carbonate.

5. 344 parts'of 4.4-diaminodiphenyl-3.3'-disulfonic acid are tetrazotized in the usual manner. An aqueous solution of 388 parts of the sodium salt of 4-acetoacetylamino-l.1'-azoben zene-4'-sulfonic acid is caused to run into the suspension of the tetrazo-compound and the solution is neutralized until a feebly acid reaction Tis' produced. The disazo-dyestuff obtained is then coupled with 427 parts of sodium 4-acetoacetylamino-Z-methoxy 4'- methyl-1,1'-azobenzene-3-su1fonate in a solution rendered alkaline The tetrakisazo-dyestuff obtained dyes cotton reddish yellow tints of very good fastness to water and to washing.

6. 462 parts of 4.4-diamino-2.2'-dimethoxydiphenylurea-5.5disulfonic acid are tetrazotized in the usual manner and coupled with 766 parts of the sodium salt of 4-acetoacetylamino-1.1- azobenzene-4'-sulfonic acid in a solution rendered alkaline with sodium carbonate. The dyestufi obtained is an orange powder which dyes cotton reddish-yellow tints of good fastness to wet-processing.

Dyestuffs of similar properties are obtained by using 4-aceto acetylamino-2-methyl-2'-chloro- 1.1-azobenzene-5-sulfonic acid or 4-acetoacetylamino-2-methoxy-4'-methyl -1.1 -azobenzene- 3'-sulfonic acid as coupling component.

We claim:

1. The water-soluble tetrakis-azodyestufi's of the following general formula:

SOaH

wherein X stands for a member of the group consisting of a simple carbon linkage, the grouping -CH=CH and the grouping NHCONH, Y stands for a member of the group consisting of hydrogen, methyl and alkoXy, Z1 stands for a member of the group consisting of the sulfonic acid and carboxylic acid groups, Z2 stands for a member of the group consisting of hydrogen, the sulfonic acid and carboxylic acid group, and Z3 and Z4 stand for members of the group consisting of hydrogen, methyl, alkoxy and chlorine groups, being yellow to orange powders which have a very good affinity for cotton, regenerated cellulose fibers and mixtures thereof and yield yellow and orange dyeings of very good fastness to water and to washing and good fastness to light.

2. The water-soluble tetrakis-azodyestufis of the following general formula:

SOzH

wherein X stands for a member of the group consisting of a simple carbon linkage, the grouping -CH=CH- and the grouping N'[-ICONH-, being yellow to orange powders which have a very good afiinity for cotton, regenerated cellulose fibers and mixtures thereof and yield yellow and orange dyeings of very good fastness to water and to washing and good iastne'ss to light.

3. The water-soluble tetrakis-azodyestufi of dyeings of very good fastness to water and to the following formula: I washing and good fastness to light.

SOaH SOzH being a yellow powder which has a very good 5. The water-soluble tetrakis-azodyestufi of afiinity for cotton, regenerated cellulose fibers the following formula:

and mixtures thereof and yields yellow dyeings being an orange powder which has a very good of very good fastness to water and to washing afiinity for cotton, regenerated cellulose fibers and good fastness to light. and mixtures thereof and yields orange dyeings 4. The water-soluble tetrakis-azodyestuff of the following formula:

SOQH SOaH being a yellow powder which has a very good of very good fastness to water and to washing afiinity for cotton, regenerated cellulose fibers and good fastness to light. and mixtures thereof and yields reddish yellow ADOLF SIEGLITZ.

MARTIN REUTER. 

